Flame-retardant epoxy composite material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of light flexible photovoltaic modules, and relates to a flame-retardant epoxy composite material as well as a preparation method and application thereof. Comprising the following components: bisphenol epoxy resin, aromatic epoxy resin, halogen-containing epoxy resin, a curing agent A, a curing agent B, a curing accelerator, a flame retardant A, a flame retardant B, a UV absorbent, a light stabilizer, an antioxidant and nano-coated montmorillonite. The nano-coated montmorillonite is added on the premise of not influencing the light transmittance, the flame retardant is matched with the montmorillonite at high temperature to generate a heat insulation carbon layer, and the montmorillonite is used as a heat insulation carbon layer reinforcing medium to play a role in condensed phase flame retardance, heat insulation, cooling and slowing down thermal degradation of resin, so that flame propagation is slowed down, and the flame retardance is effectively improved; the composite material is suitable for light flexible components with high flame resistance requirements.

Description

Technical Field

[0001] The present invention belongs to the technical field of lightweight flexible photovoltaic components, and in particular relates to a flame retardant epoxy composite material and a preparation method and application thereof. Background Art

[0002] With the wide application of lightweight flexible photovoltaic modules in the fields of BIPV and BAPV, new requirements are put forward for the flame retardancy of the packaging materials of lightweight flexible photovoltaic modules. For public buildings with limited area, the building coverings must reach the level of UL746C or above. Currently, most modules on the market are rated at C level.

[0003] WO2023212989A1 uses acrylic powder resin and ETFE film on the surface of the module. Although the ETFE film itself is flame retardant, it has a thickness of less than 50 μm and is not suitable for use at >15 kW / m 2 It will melt and fail quickly under high-power flames. Therefore, the flame retardancy level of the components designed as building coverings has not been improved.

[0004] CN104830025A uses two resins, silicone-fluorine-containing random acrylate copolymer and ester ring epoxy resin, as the matrix, and uses modified SiO2 for reinforcement. The thermal deformation temperature of the material is increased, the water absorption is reduced, and the scratch resistance is improved. However, the ester ring has a high curing temperature and a long curing time, and is only suitable for the field of electronic product packaging. In addition, the flame retardant performance is not characterized.

[0005] CN115466565B uses polyurethane acrylic acid to prepare a composite material for packaging components through a two-step process, but the carbon content of the main chain is low and the flame retardant level of coverings in the construction field cannot be achieved except by adding pure halogen flame retardants. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a flame retardant epoxy composite material and a preparation method and application thereof. The composite material effectively improves the flame retardant performance and is suitable for lightweight flexible photovoltaic modules with high flame retardancy requirements.

[0007] The present invention provides a flame retardant epoxy composite material, which comprises the following components in parts by weight: 10-40 parts of bisphenol epoxy resin; Aromatic epoxy resin 10-20 parts; 40-50 parts of halogen-containing epoxy resin; Curing agent A 4-6 parts; Curing agent B 5-10 parts; Curing accelerator 0.1-0.5 parts; Flame retardant A 5-10 parts; Flame retardant B 1-3 parts; UV absorber 0.5-1 part; Light stabilizer 0.5-1 part; Antioxidant 0.2-0.5 parts; 0.5-1 part of nano-coated montmorillonite; Wherein, the nano-coated montmorillonite comprises the following components: 1-5 parts of nano-montmorillonite; 10-30 parts of hydroxy acrylate; 5-20 parts of coating monomer; 5-10 parts of diluent; 1-5 parts of interface treatment agent; Solvent 50-70 parts.

[0008] Preferably, the bisphenol epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol S epoxy resin, and bisphenol F epoxy resin.

[0009] Preferably, the aromatic epoxy resin includes one or more of triphenylglycidyl ether methane, triglycidyl p-aminophenol, N,N,N,N-tetraglycidyl-4,4-diaminodiphenylmethane, and 4-(diglycidylamino)phenyl glycidyl ether. More preferably, the aromatic epoxy resin is triglycidyl p-aminophenol.

[0010] Preferably, the halogen-containing epoxy resin includes one or more of DGEBA epoxy resin and high-bromine flame-retardant bisphenol A epoxy resin (bromine content>20wt%).

[0011] Preferably, the curing agent A is an aromatic curing agent, such as 4,4'-diaminodiphenylmethane (DDM), metaphenylenediamine (MPD), diaminodiphenyl sulfone (DDS), 4,4'-diamino-3,3',5',5 (DTB) tetramethylbenzophenone, and the like.

[0012] Preferably, the curing agent B is a chlorine-containing aromatic diamine, such as diaminodichlorodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenyl sulfone (DCDPS), 2,4-dichloro-1,3-phenylenediamine (DCDA), etc., in order to increase the fluidity of the curing agent and reduce the viscosity of the resin.

[0013] Preferably, the curing accelerator is a boron amine complex accelerator. More preferably, the ligand of boron trifluoride in the boron amine complex is one of n-hexylamine, monoethylamine, aniline, diethylamine, piperidine, triethylamine, and aniline, and most preferably boron trifluoride ethylamine.

[0014] Preferably, the flame retardant A is hexaphenoxycyclotriphosphazene.

[0015] Preferably, the flame retardant B is a DOPO derivative, such as DOPO-hydroquinone, DOPO-phenyl vinyl phosphate, DOPO-bisphenol A, or 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide.

[0016] Preferably, the UV absorber includes one or more of triazine UV absorbers UV1164, UV1577, and UV400.

[0017] Preferably, the light stabilizer includes one or more of benzotriazole light stabilizers UV1130 and UV928.

[0018] Preferably, the antioxidant includes one or more of the hindered phenol antioxidants 1076, 1098, and 1010.

[0019] Preferably, the hydroxy acrylate includes one or more of 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, and pentaerythritol triacrylate.

[0020] Preferably, the coating monomer includes one or more of 2,2'-diallyl bisphenol A, 2,2'-diallyl bisphenol S, and epoxy acrylate.

[0021] Preferably, the diluent includes one or more of methyl methacrylate, butyl methacrylate, and isobornyl methacrylate.

[0022] Preferably, the interface treatment agent includes one or more of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltriethoxysilane.

[0023] Preferably, the solvent is anhydrous ethanol.

[0024] The present invention also provides a method for preparing a flame retardant epoxy composite material, comprising the following steps: (1) According to the ratio, nano-montmorillonite is ultrasonically dispersed in a solvent to obtain a nano-montmorillonite solution; then, hydroxy acrylate, coating monomer, diluent, and interface treatment agent are added to the nano-montmorillonite solution, and after the temperature is raised to 70-80° C., an initiator solution is added to react, and after the reaction, the solvent is evaporated and dried to obtain nano-coated montmorillonite; (2) According to the proportion, bisphenol epoxy resin, aromatic epoxy resin, halogen-containing epoxy resin, flame retardant A, flame retardant B, UV absorber, light stabilizer and antioxidant are added into a stirring kettle, heated to 120-130° C. and stirred to obtain main agent A; (3) The curing agent A, the curing agent B, the curing accelerator and the nano-coated montmorillonite in step (1) are mixed and ground, and then added to the main agent A at 80-90° C. to obtain a flame retardant epoxy composite material.

[0025] Preferably, the initiator in step (1) is one or more of benzoyl peroxide, azobisisobutyronitrile, diisopropylbenzene peroxide, tert-butyl hydroperoxide, and tert-butyl perbenzoate; the amount of the initiator added is 0.1%-0.5% of the total mass of the system; and the solvent of the initiator solution is anhydrous ethanol.

[0026] The present invention also provides an application of a flame-retardant epoxy composite material in a lightweight flexible photovoltaic module.

[0027] Beneficial Effects (1) The present invention adds nano-coated montmorillonite without affecting the transmittance. The flame retardant combines with the montmorillonite at high temperature to form a heat-insulating carbon layer. The montmorillonite serves as a reinforcing medium for the heat-insulating carbon layer, plays a role in condensed phase flame retardancy, heat insulation and cooling, and slows down the thermal degradation of the resin, thereby slowing down the flame propagation, effectively improving the flame retardant performance, and is suitable for lightweight flexible components with high flame retardancy requirements.

[0028] (2) The present invention uses curing agent B to lower the melting point of curing agent A, which is beneficial to resin blending and is combined with a curing accelerator to achieve medium-temperature rapid curing.

[0029] (3) The present invention uses halogen-containing epoxy resin as a diluent to reduce the viscosity of the resin system. After the reaction, the stable halogen side groups can cause rapid isomerization of the molecular chain, thereby delaying the degradation of the epoxy resin at high temperature.

[0030] (4) The present invention uses flame retardant B and flame retardant A to synergistically enhance the effect, have good compatibility, and do not migrate under high temperature and high humidity conditions. DETAILED DESCRIPTION

[0031] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0032] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0033] Table 1 Formula of nano-coated montmorillonite (parts by weight)

[0034] The preparation method of the nano-coated montmorillonite comprises the following steps: 1. Ultrasonic dispersion of nano-montmorillonite particles in anhydrous ethanol for 1 h to ensure uniform dispersion of the particles; 2. Add hydroxy acrylate, coating monomer, diluent and interface treatment agent into a three-hole flask according to the proportion, mix for 10 minutes under nitrogen atmosphere, and raise the temperature of the reactants to 70°C; 3. The initiator was dripped into the reactants within 20 minutes, and a viscous paste polymer was generated after 20 minutes; 4. Then, the solvent is evaporated off, dried and crushed to obtain nano-coated montmorillonite.

[0035] Table 2 Formula of flame retardant epoxy composite material (parts by weight)

[0036] Table 3 Formula of flame retardant epoxy composite material (parts by weight)

[0037] The method for preparing the flame retardant epoxy composite material comprises the following steps: (1) According to the proportion, bisphenol epoxy resin, aromatic epoxy resin, halogen-containing epoxy resin, flame retardant A, flame retardant B, UV absorber, light stabilizer and antioxidant are added into a stirring kettle, heated to 120°C and stirred for 20 minutes. After stirring evenly, vacuum is applied and the temperature is gradually reduced to 80°C to obtain main agent A; (2) Curing agent A, curing agent B, curing accelerator and nano-coated montmorillonite were mixed and ground (the particle size was 150 μm as measured by a scraper particle size meter), and then added to the main agent A at 80° C., stirred and evacuated to obtain a flame-retardant epoxy composite material.

[0038] The flame retardant epoxy composite material is used to prepare prepreg and samples, comprising the following steps: 1. Gluing: Put the above epoxy resin into the glue coating machine and prepare a 50~60g / m 2 Adhesive film, coating temperature 80℃; 2. Composite: 160g / m 2 The glass fiber woven cloth is unrolled and the prepreg is prepared by 2 coatings and 1 dipping. The rolling temperature is 100°C, 4 groups of rollers are used, and the rolling line speed is less than 3m / min to make the prepreg; 3. Preparation of composite material samples: The prepreg was packaged under the conditions of 0.9atm vacuum and 143℃ / 15min curing, and the composite material performance was tested.

[0039] Table 4 Performance test results of flame retardant epoxy composites

[0040] Table 5 Performance test results of flame retardant epoxy composites

Claims

1. A flame retardant epoxy composite material, characterized in that: The composite material comprises the following components in parts by weight: 10-40 parts of bisphenol epoxy resin; 10-20 parts of aromatic epoxy resin; 40-50 parts of halogen-containing epoxy resin; 4-6 parts of curing agent A; Curing agent B 5-10 parts; 0.1-0.5 parts of curing accelerator; 5-10 parts of flame retardant A; Flame retardant B 1-3 parts; UV absorber 0.5-1 part; Light stabilizer 0.5-1 part; 0.2-0.5 parts of antioxidant; 0.5-1 part of nano-coated montmorillonite; Wherein, the nano-coated montmorillonite comprises the following components: 1-5 parts of nano-montmorillonite; 10-30 parts of hydroxy acrylate; 5-20 parts of coating monomer; 5-10 parts of diluent; 1-5 parts of interface treatment agent; 50-70 parts of solvent.

2. The flame-retardant epoxy composite material according to claim 1, characterized in that: The bisphenol-type epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol S epoxy resin, and bisphenol F epoxy resin; the aromatic epoxy resin includes one or more of triphenyl glycidyl ether methane, triglycidyl p-aminophenol, N,N,N,N-tetraglycidyl-4,4-diaminodiphenylmethane, and 4-(diglycidylamino)phenyl glycidyl ether; the halogen-containing epoxy resin includes one or more of DGEBA epoxy resin and high-bromine flame-retardant bisphenol A epoxy resin.

3. The flame-retardant epoxy composite material according to claim 1, characterized in that: The curing agent A is a curing agent containing an aromatic group; the curing agent B is a chlorine-containing aromatic diamine; and the curing accelerator is a boron amine complex accelerator.

4. The flame-retardant epoxy composite material according to claim 1, characterized in that: The flame retardant A is hexaphenoxycyclotriphosphazene; and the flame retardant B is a DOPO derivative.

5. The flame-retardant epoxy composite material according to claim 1, characterized in that: The UV absorber includes one or more of triazine UV absorbers UV1164, UV1577, and UV400; the light stabilizer includes one or more of benzotriazole light stabilizers UV1130 and UV928; and the antioxidant includes one or more of hindered phenol antioxidants 1076, 1098, and 1010.

6. The flame-retardant epoxy composite material according to claim 1, characterized in that: The hydroxy acrylate includes one or more of 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, and pentaerythritol triacrylate.

7. The flame-retardant epoxy composite material according to claim 1, characterized in that: The coating monomer includes one or more of 2,2'-diallyl bisphenol A, 2,2'-diallyl bisphenol S, and epoxy acrylate.

8. The flame-retardant epoxy composite material according to claim 1, characterized in that: The diluent includes one or more of methyl methacrylate, butyl methacrylate, and isobornyl methacrylate; the interface treatment agent includes one or more of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltriethoxysilane; and the solvent is anhydrous ethanol.

9. A method for preparing the flame-retardant epoxy composite material according to any one of claims 1 to 8, comprising the following steps: (1) According to the ratio, nano-montmorillonite is ultrasonically dispersed in a solvent to obtain a nano-montmorillonite solution; then, hydroxy acrylate, coating monomer, diluent, and interface treatment agent are added to the nano-montmorillonite solution, and after the temperature is raised to 70-80°C, an initiator solution is added to react, and after the reaction, the solvent is evaporated and dried to obtain nano-coated montmorillonite; (2) According to the proportion, bisphenol epoxy resin, aromatic epoxy resin, halogen-containing epoxy resin, flame retardant A, flame retardant B, UV absorber, light stabilizer, and antioxidant are added into a stirring kettle and heated to 120-130°C and stirred to obtain main agent A; (3) Curing agent A, curing agent B, curing accelerator, and nano-coated montmorillonite in step (1) are mixed and ground, and then added to the main agent A at 80-90° C. to obtain a flame retardant epoxy composite material.

10. Use of the flame-retardant epoxy composite material according to any one of claims 1 to 8 in a lightweight flexible photovoltaic module.

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